Molecular tuning boosts asymmetric C-C coupling for CO conversion to acetate

Jie Ding; Fuhua Li; Xinyi Ren; Yuhang Liu; Yifan Li; Zheng Shen; Tian Wang; Weijue Wang; Yang-Gang Wang; Yi Cui; Hongbin Yang; Tianyu Zhang; Bin Liu

doi:10.1038/s41467-024-47913-1

Molecular tuning boosts asymmetric C-C coupling for CO conversion to acetate

Nat Commun. 2024 Apr 29;15(1):3641. doi: 10.1038/s41467-024-47913-1.

Authors

Jie Ding^#¹, Fuhua Li^#¹, Xinyi Ren², Yuhang Liu³, Yifan Li⁴, Zheng Shen², Tian Wang⁵, Weijue Wang², Yang-Gang Wang⁶, Yi Cui⁴, Hongbin Yang⁷, Tianyu Zhang⁸, Bin Liu^{9

10}

Affiliations

¹ Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong SAR, China.
² CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
³ School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, China.
⁴ Vacuum Interconnected Nanotech Workstation, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, China.
⁵ Department of Chemical & Biomolecular Engineering, National University of Singapore, Singapore, Singapore.
⁶ Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, China.
⁷ School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, China. hbyang@dicp.ac.cn.
⁸ College of Environmental Science and Engineering, Beijing Forestry University, Beijing, China. tzhang@bjfu.edu.cn.
⁹ Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong SAR, China. bliu48@cityu.edu.hk.
¹⁰ Department of Chemistry & Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong SAR, China. bliu48@cityu.edu.hk.

^# Contributed equally.

Abstract

Electrochemical carbon dioxide/carbon monoxide reduction reaction offers a promising route to synthesize fuels and value-added chemicals, unfortunately their activities and selectivities remain unsatisfactory. Here, we present a general surface molecular tuning strategy by modifying Cu₂O with a molecular pyridine-derivative. The surface modified Cu₂O nanocubes by 4-mercaptopyridine display a high Faradaic efficiency of greater than 60% in electrochemical carbon monoxide reduction reaction to acetate with a current density as large as 380 mA/cm² in a liquid electrolyte flow cell. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy reveals stronger *CO signal with bridge configuration and stronger *OCCHO signal over modified Cu₂O nanocubes by 4-mercaptopyridine than unmodified Cu₂O nanocubes during electrochemical CO reduction. Density function theory calculations disclose that local molecular tuning can effectively regulate the electronic structure of copper catalyst, enhancing *CO and *CHO intermediates adsorption by the stabilization effect through hydrogen bonding, which can greatly promote asymmetric *CO-*CHO coupling in electrochemical carbon monoxide reduction reaction.